Zeolite Y alkylation catalysts

ABSTRACT

The present invention is directed to a zeolite Y catalyst having a controlled macropore structure. The present invention is also directed to a zeolite Y catalyst composite and a process for preparing the catalyst composite. The catalyst composite exhibits reduced deactivation rates during the alkylation process, thereby increasing the life of the catalyst. The present invention is also directed to processes for the preparation of carbonated, overbased aromatic sulfonates, which processes comprise alkylation, carbonation of aromatic hydrocarbons with one or more olefins.

This application is Continuation of application Ser. No. 10/800,047,filed Mar. 12, 2004.

FIELD OF THE INVENTION

The present invention is directed to a zeolite Y catalyst having acontrolled macropore structure. The present invention is also directedto a catalyst composite comprising zeolite Y and a process for preparingthe catalyst composite. The present invention is also directed toalkylation of aromatic hydrocarbons using the catalysts and the catalystcomposites of this invention, and the sulfonation and carbonation of thealkylated aromatic hydrocarbons. The catalysts and the catalystcomposites exhibit reduced deactivation rates during the alkylationprocess, thereby increasing the life of the catalyst.

BACKGROUND OF THE INVENTION

It is well known to catalyze the alkylation of aromatics with a varietyof Lewis or Bronsted acid catalysts. Typical commercial catalystsinclude phosphoric acid/kieselguhr, aluminum halides, boron trifluoride,antimony chloride, stannic chloride, zinc chloride, onium poly(hydrogenfluoride), and hydrogen fluoride. Alkylation with lower molecular weightolefins, such as propylene, can be carried out in the liquid or vaporphase. For alkylations with higher olefins, such as C₁₆ olefins, thealkylations are done in the liquid phase, usually in the presence ofhydrogen fluoride. Alkylation of benzene with higher olefins isespecially difficult, and requires hydrogen fluoride treatment. However,hydrogen fluoride is not environmentally attractive.

The use of the above listed acids is extremely corrosive, thus requiringspecial handling and equipment. Also, the use of these acids mightinvolve environmental problems. Another problem is that the use of theseacids can give less than desirable control on the precise chemicalcomposition of the product produced. Thus, it would be preferable to usea safer, simpler catalyst, preferably in solid state. This simplerprocess would result in less capital investment, which would result in aless expensive product.

Solid crystalline aluminosilicate zeolite catalysts have been known tobe effective for the alkylation of aromatics with olefins. Zeoliticmaterials which are useful as catalysts are usually inorganiccrystalline materials that possess uniform pores with diameters in themicropore range that is less than 20 angstroms. Zeolites occur naturallyand may also be prepared synthetically. Synthetic zeolites include, forexample, zeolites A, X, Y, L and omega. It is also possible to generatemetaloaluminophosphates and metalosilicophosphates. Other materials,such as boron, gallium, iron or germanium, may also be used to replacethe aluminum or silicon in the framework structure.

These zeolite catalyst materials are commercially available as finecrystalline powders for further modification to enhance their catalyticproperties for particular applications. Processes for the furthermodification to enhance catalytic properties of the crystalline zeolitecatalysts are well known in the art, such as forming the zeolitecatalysts into shaped particles, exchanging the cations in the catalystmatrix, etc.

Forming the zeolite powders into shaped particles may be accomplished byforming a gel or paste of the catalyst powder with the addition of asuitable binder material such as a clay, an inorganic compound, or anorganic compound and then extruding the gel or paste into the desiredform. Zeolite powders may also be formed into particles without the useof a binder. Typical catalyst particles include extrudates whose crosssections are circular or embrace a plurality of arcuate lobes extendingoutwardly from the central portion of the catalyst particles.

One problem with catalyst particles used in fixed bed reactors iscatalyst deactivation. In most hydrocarbon conversion processes,including alkylation, the primary catalyst deactivation is caused bycoke formation. This catalyst deactivation is a serious problem in theuse of zeolite catalysts for alkylation reactions. This deactivationproblem is well known in the art and it is well understood that thedeactivation mechanism can involve polymerization of the olefin intolarge molecular species that cannot diffuse out of the pores containingthe active sites in the zeolitic material.

The use of zeolite catalysts for preparation of alkyl aromatics istypically conducted by the catalytic alkylation of aromatic hydrocarbonswith normal alpha olefins or branched-chain olefins, and optionally apromotor. The alkylated aromatic hydrocarbons can be converted intocorresponding sulfonic acids which can be further converted intoalkylated aromatic sulfonates.

A number of patents have discussed processes for the preparation ofzeolite catalysts and the further shaping and forming of the catalystparticles and extrudates with and without the use of binders. There arealso a number of patents disclosing the use of zeolite catalysts foralkylation of aromatic hydrocarbons.

U.S. Pat. No. 3,094,383 discloses the preparation of synthetic zeolitematerials which upon hydration yield a sorbent of controlled effectivepore diameter and in which the sorbent and its zeolite precursor areprovided directly in the form of an aggregate.

U.S. Pat. No. 3,130,007 discloses the method of preparing sodium zeoliteY with silica to alumina ratios ranging from greater than 3 to about3.9.

U.S. Pat. No. 3,119,660 discloses a process for making massive bodies orshapes of crystalline zeolites. The patent also discloses methods forthe identification of the catalyst materials using X-ray powderdiffraction patterns in conjunction with chemical analyses.

U.S. Pat. No. 3,288,716 discloses that the high “heavy content” of thealkylated aromatic product can be controlled during the alkylation stepand has advantages over distilling the alkylated aromatic product toobtain the desired molecular weight.

U.S. Pat. Nos. 3,641,177 and 3,929,672 disclose the technique to removesodium or other alkali metal ions from zeolite catalysts. The '177patent also discloses that such removal of the sodium or other alkalimetal ions activates the zeolite catalysts for the alkylation ofaromatic hydrocarbons with olefins by liquid phase reaction.

U.S. Pat. Nos. 3,764,533; 4,259,193 and 5,112,506 disclose the “heavycoulealkylate” content influences neutral sulfonates and overbasedsulfonates. In U.S. Pat. No. 5,112,506, the effect of molecular weightdistribution or “heavy alkylate” is shown to influence the performanceof both Neutral and HOB sulfonates and the di-alkylate content is shownto influence the rust performance of the corresponding sulfonate in U.S.Pat. No. 3,764,533. In U.S. Pat. No. 4,259,193, a mono-alkylatesulfonate is preferred. U.S. Pat. Nos. 3,288,716; 3,764,533; 4,259,193and 5,112,506 are hereby incorporated by reference for all purposes.

U.S. Pat. No. 3,777,006 discloses the use of nucleating centers for thecrystallization of crystalline aluminosilicate zeolites having a size inexcess of 200 microns and characterized by high strength and excellentadsorptive properties.

U.S. Pat. No. 4,185,040 discloses the preparation of highly stable andactive catalysts for the alkylation of aromatic hydrocarbons with C₂-C₄olefins. The catalysts are acidic crystalline aluminosilicate zeoliteswhich exhibit much improved deactivation rates.

U.S. Pat. No. 4,395,372 discloses an alkylation process for alkylatingbenzene comprising contacting benzene and lower olefins with a rareearth exchanged X or Y zeolite catalyst in the presence of sulfurdioxide.

U.S. Pat. No. 4,570,027 discloses the use of a low crystallinity,partially collapsed zeolite catalyst for producing alkylaromatichydrocarbons. The alkylation reaction also involves conditioning thecatalyst bed with hydrogen prior to conducting the alkylation reaction.

U.S. Pat. Nos. 4,762,813; 4,767,734; 4,879,019 and 5,111,792 disclosethe preparation of a hydrocarbon conversion catalyst using a low silicato alumina ratio zeolite Y bound into an extrudate and steamed to modifythe catalyst.

U.S. Pat. No. 4,764,295 discloses a process for making non-foamingdetergent-dispersant lubricating oil additives. The process furtherinvolves carbonation for making the products more basic.

U.S. Pat. No. 4,876,408 discloses an alkylation process using anammonium-exchanged and steam stabilized zeolite Y catalyst having anincreased selectivity for mono-alkylation the process involves thepresence of at least one organic compound under conditions such thatsufficient amount of carbonaceous material evenly deposits on thealkylation catalyst to substantially suppress its alkylation activity.

U.S. Pat. No. 4,916,096 discloses use of a zeolite Y catalyst forhydroprocessing. The zeolite Y catalyst comprises a modified crystallinealuminosilicate zeolite Y, a binder and at least one hydrogenationcomponent of a Group VI or a Group VIII metal.

U.S. Pat. No. 5,026,941 discloses the use of a zeolite Y catalyst havinga silica to alumina molar ratio of 15 to 110 for the alkylation ofnaphthalene or mono-isopropylnaphthalene.

U.S. Pat. No. 5,118,896 discloses an aromatic alkylation processcomprising the steps of contacting an aromatic hydrocarbon feed with analkylating agent under liquid phase alkylation conditions in thepresence of a silica-containing large macropore, small particle sizezeolite catalyst, the catalyst having a pore volume of about 0.25 to0.50 cc/g in pores having a radius of 450 angstroms and a catalystparticle diameter of not more than 1/32 of an inch.

U.S. Pat. No. 5,191,135 discloses the process for making long-chainalkyl-substituted aromatic compounds from naphthalenes, the processcomprising a zeolite alkylation catalyst in the presence of 0.5 to 3.0weight percent water. The presence of water increases the selectivityfor making mono-alkylated products.

U.S. Pat. Nos. 5,240,889 and 5,324,877 disclose processes for thepreparation of a catalyst composition having alkylation and/ortransalkylation activity and wherein the catalyst composition containsgreater than 3.5 weight percent water based on the total weight of thecatalyst composition and the aromatic alkylation process using saidcatalyst composition and olefins containing 2 carbon atoms to 25 carbonatoms.

U.S. Pat. No. 5,506,182 discloses the preparation of a catalystcomposition comprising 10 to 90 percent of a modified zeolite Y catalystformed from a modified zeolite Y and 10 to 90 percent binder usingslurries of the modified zeolite Y and the binder to form the catalystcomposition having a clear absorption peak in an IR spectrum of awavelength of 3602 per centimeter. The patent also discloses thesubstitution of iron for the alumina in the zeolite Y structure.

U.S. Pat. No. 5,922,922 discloses a process for isomerizing a normalalpha olefin in the presence of an acidic catalyst having aone-dimensional pore system, and then using of the isomerized olefin toalkylate aromatic hydrocarbons in the presence of a second acidiccatalyst, which can be zeolite Y having a silica to alumina ratio of atleast 40 to 1.

U.S. Pat. No. 5,939,594 discloses the preparation of a superalkalinizedalkylaryl sulfonate of alkaline earth metal. The alkyl group of thealkylaryl sulfonate contains between 14 to 40 carbon atoms and the arylsulfonate radical of alkaline earth metal is fixed in a molar proportioncomprised between 0 and 13% in positions 1 or 2 of the linear alkylchain.

U.S. Pat. No. 6,031,144 discloses a process for reducing the residualolefin content of an alkylation reaction product by removing at least aportion of the non-alkylated single-ring aromatic hydrocarbon and thenreacting the remaining alkylation reaction product in the presence of anacidic catalyst such as a molecular sieve or clay.

U.S. Pat. No. 6,337,310 discloses the preparation of alkylbenzene frompreisomerized normal alpha olefins for making low overbased and highoverbased sulfonates having a TBN in the range of 3 to 500. The processuses HF as catalyst or a solid acidic alkylation catalyst, such as azeolite having an average pore size of at least 6 angstroms.

It is known that most solid acid catalysts produce high 2-arylattachment when alkylating with alpha-olefins. See S. Sivasanker, A.Thangaraj, “Distribution of Isomers in the Alkylation of Benzene withLong-Chain Olefins over Solid Acid Catalysts,” Journal of Catalysis,138, 386-390 (1992).

Two general treatises on zeolite are; Handbook of Molecular Sieves byRosemarie Szostak (Van Nostrand Reinhold, New York 1992) and MolecularSieves: Principles of Synthesis and Identification, 2^(nd) Edition, byRosemarie Szostak (Chapman and Hall, London, UK 1999).

SUMMARY OF THE INVENTION

The present invention is directed to zeolite Y catalysts having acontrolled macropore structure. The present invention is also directedto catalyst composites comprising zeolite Y catalyst and a process forpreparing the catalyst composites. The catalysts and catalyst compositesexhibit reduced deactivation rates during the alkylation process,thereby increasing the life of the catalysts and catalyst composites.The present invention is also directed to processes for preparation ofcarbonated, overbased alkylated aromatic sulfonates, which processescomprise the alkylation in the presence of the catalysts and catalystcomposites of this invention, and further sulfonation and carbonation,overbasing of alkylated aromatic hydrocarbons.

In particular, the present invention is directed to a catalyst having amacropore structure comprising zeolite Y wherein the peak macroporediameter of the catalyst, measured by ASTM Test No. D 4284-03, is lessthan or equal to about 2000 angstroms, and the cumulative pore volume atpore diameters less than or equal to about 500 angstroms, measured byASTM Test No. D 4284-03, is less than or equal to about 0.30 millilitersper gram, preferably less than about 0.30 milliliters per gram at porediameters less than or equal to about 400 angstroms, and more preferablyin the range of about 0.05 milliliters per gram to about 0.18milliliters per gram at pore diameters less than or equal to about 400angstroms.

The cumulative pore volume of the zeolite Y catalyst at pore diametersless than or equal to about 300 angstroms is preferably less than about0.25 milliliters per gram, more preferably at pore diameters less thanor equal to about 300 angstroms is less than about 0.20 milliliters pergram, and most preferably at pore diameters less than or equal to about300 angstroms is in the range of about 0.08 milliliters per gram toabout 0.16 milliliters per gram.

Preferably the peak macropore diameter of the zeolite Y catalyst is inthe range of about 700 angstroms to about 1800 angstroms, and morepreferably the peak macropore diameter is in the range of about 750angstroms to about 1600 angstroms, and most preferably the peakmacropore diameter is in the range of about 800 angstroms to about 1400angstroms.

The zeolite Y catalyst of the present invention may have silica toalumina ratio of about 5:1 to about 100:1, preferably the silica toalumina ratio is from about 30:1 to about 80:1, and most preferably thesilica to alumina ratio is from about 50:1 to about 70:1.

In an embodiment of the zeolite Y catalyst of the present invention, thecatalyst is in the form of a tablet. The tablet may or may not include abinder. Preferably the peak macropore diameter of the zeolite Y catalysttablet is in the range of about 500 angstroms to about 1500 angstroms,and the cumulative pore volume at pore diameters less than or equal toabout 500 angstroms is in the range of about 0.05 milliliters per gramto about 0.15 milliliters per gram.

An embodiment of the present invention is directed to a catalystcomposite comprising:

-   -   (a) the zeolite Y catalyst of the above invention; and    -   (b) a binder.

The binder in (b) above is a suitable inorganic material, preferably thebinder is alumina.

The zeolite Y in the catalyst composite of the above embodiment is inthe range of about 40 weight percent to about 99 weight percent based onthe total dry weight of the catalyst composite. Preferably, zeolite Y inthe catalyst composite is in the range of about 50 weight percent toabout 85 weight percent based on the total dry weight of the catalystcomposite.

A further embodiment of the present invention is directed to the processfor preparing a catalyst composite comprising the steps of:

-   -   (a) contacting a zeolite Y powder with a binder in the presence        of volatiles to form a mixture wherein the weight ratio of the        zeolite Y is in the range of about 40 to about 99 based on the        total dry weight of the resulting catalyst composite, and        wherein the volatiles in the mixture are in the range of about        30 weight percent to about 70 weight percent;    -   (b) shaping the mixture to form a composite;    -   (c) drying the composite; and    -   (d) calcining the composite in a substantially dry environment.

The shaping in step (b) in the above process preferably comprisesextruding.

The above process further comprises addition of a shaping aid in step(a). Preferably, the shaping aid is a polysaccharide.

The binder in step (a) above is a suitable inorganic material,preferably the binder is alumina.

The volatiles in step (a) in the process for making the zeolite Ycomposite comprise water and an acid, and preferably the acid is nitricacid.

The volatiles in step (a) in the above process for making the zeolite Ycomposite further comprise a polysaccharide.

The volatiles in the mixture in step (a) in the process for making thezeolite Y composite are in the range of about 40 weight percent to about60 weight percent of the mixture.

In step (a) of the above process, the weight percent of the zeolite Y isin the range of about 50 to about 85.

A further embodiment of the present invention is directed to a catalystcomposite made by the above process.

Another embodiment of the present invention is directed to a process formaking an alkylated aromatic composition comprising contacting at leastone aromatic hydrocarbon with at least one olefin under alkylationconditions in the presence of a catalyst having a macropore structurecomprising zeolite Y wherein the peak macropore diameter of thecatalyst, measured by ASTM Test No. D 4284-03, is less than or equal toabout 2000 angstroms and cumulative pore volume of the catalyst at porediameters less than or equal to about 500 angstroms, measured by ASTMTest No. D 4284-03, is equal to or less than about 0.30 milliliters pergram.

The above alkylation process is conducted without the addition of waterand using dried aromatic hydrocarbon and olefin feed. It is believedthat the presence of water during the alkylation increases thedeactivation rate of the catalysts of this invention.

The above alkylation process further comprises sulfonating the alkylatedaromatic composition to form an alkylated aromatic sulfonic acid.

The above process further comprises reacting the alkylated aromaticsulfonic acid an alkaline earth metal and carbon dioxide to produce acarbonated, overbased alkylated aromatic sulfonate.

Yet a further embodiment of the present invention is directed to aprocess for making an alkylated aromatic composition comprisingcontacting at least one aromatic hydrocarbon with at least one olefinunder alkylation conditions in the presence of a catalyst compositecomprising zeolite Y, and wherein the catalyst composite is prepared bythe above process.

The aromatic hydrocarbon of the above process is benzene, toluene,xylene, cumene, or mixtures thereof. Preferably, the aromatic is benzeneor toluene.

The olefin in the above process may be an alpha olefin, an isomerizedolefin, a branched-chain olefin, or mixtures thereof. The olefin mayhave from about 4 carbon atoms to about 80 carbon atoms. The alphaolefin or the isomerized olefin may have from about 6 carbon atoms toabout 40 carbon atoms, preferably from about 20 carbon atoms to about 40carbon atoms. The branched-chain olefin may have from about 6 carbonatoms to about 70 carbon atoms, preferably from about 8 carbon atoms toabout 50 carbon atoms, and more preferably from about 12 carbon atoms toabout 18 carbon atoms.

The olefin in the above process may be a partially-branched-chain olefincontaining from about 6 carbon atoms to about 40 carbon atoms,preferably from about 20 carbon atoms to about 40 carbon atoms.

The above alkylation process further comprises sulfonating the alkylatedaromatic composition to form an alkylated aromatic sulfonic acid.

The above process further comprises reacting the alkylated aromaticsulfonic acid an alkaline earth metal and carbon dioxide to produce acarbonated, overbased alkylated aromatic sulfonate.

Yet a further embodiment of the present invention is directed to aprocess for making an alkylated aromatic composition comprisingcontacting at least one aromatic hydrocarbon with at least one olefinunder alkylation conditions in the presence of a catalyst compositecomprising zeolite Y, and wherein the catalyst composite is prepared bythe above process.

The aromatic hydrocarbon of the above process is benzene, toluene,xylene, cumene, or mixtures thereof. Preferably, the aromatic is benzeneor toluene.

The olefin in the above process may be an alpha olefin, an isomerizedolefin, a branched-chain olefin, or mixtures thereof. The olefin mayhave from about 4 carbon atoms to about 80 carbon atoms. The alphaolefin or the isomerized olefin may have from about 6 carbon atoms toabout 40 carbon atoms, preferably from about 20 carbon atoms to about 40carbon atoms. The branched-chain olefin may have from about 6 carbonatoms to about 70 carbon atoms, preferably from about 8 carbon atoms toabout 50 carbon atoms, and more preferably from about 12 carbon atoms toabout 18 carbon atoms.

The olefin in the above process may be a partially-branched-chain olefincontaining from about 6 carbon atoms to about 40 carbon atoms,preferably from about 20 carbon atoms to about 40 carbon atoms.

The above alkylation process is conducted without the addition of waterand preferably using dried aromatic hydrocarbon and olefin feed. It isbelieved that the presence of water during the alkylation increases thedeactivation rate of the catalysts of this invention.

The above alkylation process further comprises sulfonating the alkylatedaromatic composition to form an alkylated aromatic sulfonic acid.

The above process further comprises reacting the alkylated aromaticsulfonic acid an alkaline earth metal and carbon dioxide to produce acarbonated, overbased alkylated aromatic sulfonate.

The process of the above embodiment of the present invention for makingan alkylated aromatic composition further comprises the step ofisomerizing normal alpha olefin with an isomerizing acidic catalystbefore contacting the aromatic with the olefin to prepare an alkylaromatic product where less than 40 weight percent of the alkylatedaromatic hydrocarbon is 2-aryl, and at least 20 weight percent,preferably at least 75 weight percent of the alkylated aromatichydrocarbon is a mono-alkylate.

Preferably, the acidic catalyst in the isomerization step is a solidcatalyst having at least one metal oxide, which has an average pore sizeof less than 5.5 angstroms. More preferably, that acidic catalyst is amolecular sieve with a one-dimensional pore system.

DETAILED DESCRIPTION OF THE INVENTION DEFINITIONS

The term “alkylate” means an alkylated aromatic hydrocarbon.

The term “2-aryl content” is defined as the percentage of total alkylate(the alkylate species in which the alkyl chain attached to the aromaticring is derived from the olefin employed in the present alkylationprocess) that is comprised of those chemical species in which theattachment of the alkyl chain to the aromatic ring is at the 2-positionalong the alkyl chain.

The term “binder” means any suitable inorganic material which can serveas matrix or porous matrix to bind the zeolite particles into a moreuseful shape.

The term “branched-chain olefins” means olefins derived from thepolymerization of olefin monomers higher than ethylene and containing asubstantial number of branches wherein the branches are alkyl groupshaving from about one carbon atom to about 30 carbon atoms. Mixtures ofethylene and higher olefins are also contemplated.

The term “calcining” as used herein means heating the catalyst to about400° C. to about 1,000° C. in a substantially dry environment.

The term “carbonated, overbased” is used to describe those alkalineearth metal alkyl aromatic sulfonates in which the ratio of the numberof equivalents of the alkaline earth metal moiety to the number ofequivalents of the aromatic sulfonic acid moiety is greater than one,and is usually greater than 10 and may be as high as 20 or greater.

The term “centrate” refers to a mixture of sludge fractions that werecollected from prior carbonation, overbasing of alkylbenzene sulfonicacids similar to the sulfonic acids of the present invention. Centratewas produced during the purification of high TBN carbonated, overbasedsynthetic sulfonates by centrifugation and decantation at the end of thecarbonation, overbasing reaction. Centrate was added to the carbonation,overbasing of alkylbenzene sulfonic acid reaction mixture in Example 11in this patent application for recycling the contents of the centrate.Prior to its addition to the reaction mixture in Example 11, thecentrate was characterized by determination of its TBN, the amount ofxylene solvent, active calcium sulfonate, calcium hydroxide, calciumcarbonate, carbon dioxide and 100 Neutral diluent oil.

The term “cumulative pore volume” obtained by Mercury IntrusionPorosimetry as used herein refers to that part of the total volume inmilliliters per gram derived from the graphical, cumulative pore volumedistribution, measured by Section 14.1.6 of ASTM D 4284-03, or thecorresponding tabular presentation of the same data between definedupper and lower pore diameters. When no lower diameter limit is defined,the lower limit is the lowest detection limit or lowest radius measuredby Section 14.1.6 of ASTM D 4284-03.

The terms “dry basis”, “anhydrous basis”, and “volatiles-free basis”shall refer to the dry weight of catalyst composite or raw materialsexpressed on a metal oxides basis such as Na₂O.Al₂O₃._(x)SiO₂.

The term “loss-on-ignition (LOI)” as used herein means the percentweight loss of the zeolite composite or raw material samples when theyare heated to 538° C. for 1 hour. When the temperature is greater thanor equal to about 538° C., the “loss-on-ignition” approximates thepercent volatiles.

The terms “macropore”, “mesopore”, and “micropore” as used herein followthe definitions set forth by the International Union of Pure and AppliedChemistry (IUPAC), Division of Physical Chemistry, in Manual of Symbolsand Terminology for Physicochemical Quantities and Units, Appendix IIDefinitions, Terminology and Symbols in Colloid and Surface ChemistryPart I, Adopted by the IUPAC Council at Washington, D.C., U.S.A., on 23Jul., 1971. Pores with widths or diameters exceeding ˜50 nanometers (500angstroms) are called “macropores”. Pores with widths or diameters notexceeding ˜2.0 nanometers (20 angstroms) are called “micropores”. Poresof intermediate size (2.0 nanometers<width or diameter≦50 nanometers)are called “mesopores”.

The term “Mercury Intrusion Porosimetry” refers to the ASTM Test No. D4284-03 used to determine pore volume distribution of catalysts byMercury Intrusion Porosimetry. Mercury pore distribution was measuredusing a Quantachrome Scanning Mercury Porosimeter Model SP-100. Thesoftware version used by the instrument is V2.11 (dated Oct. 27, 1993).Surface tension used in the calculation is 473 dynes per centimeter andthe contact angle is 140 degrees.

The terms “normal alpha olefin” and “linear alpha olefin” mean thosestraight-chain olefins without a significant degree of alkyl branchingin which the carbon to carbon double bond resides primarily at the endor “alpha” position of the carbon chain, i.e., between C₁ and C₂. Normalalpha olefins are derived from polymerization of ethylene.

The term “normal alpha olefin isomerization” means the conversion ofnormal alpha olefins into isomerized olefins having a lower alpha olefincontent (the double bond is between C₁ and C₂), higher internal olefincontent (the double bond is in positions other than between C₁ and C₂),and optionally a higher degree of branching.

The term “partially-branched chain olefin” is defined as the olefinproduct of isomerization of normal alpha olefins wherein the degree ofbranching is higher than in the starting normal alpha olefins.

The term “peak macropore diameter” as used herein means the peakdiameter (i.e., the diameter within the macropore region at which thedifferential plot of pore size distribution, as defined by Section 14.2,reaches a maximum) in the macropore range determined by ASTM Test No. D4284-03 for the macropore peak in the catalysts of the presentinvention.

The term “peptizing” means the dispersion of large aggregates of binderparticles, including hydrated aluminas, into much smaller primaryparticles by the addition of acid.

The term “percent volatiles” as used herein means the difference betweenthe actual weight of the catalyst composite or the raw materials and theweight of the material on a dry, anhydrous, or volatiles-free basis,expressed as a percentage of the actual sample weight.

The terms “SAR” or “silica to alumina ratio” refer to the molar ratio ofsilicon oxide to aluminum oxide; mol SiO₂:mol AlO₃.

The term “sufficient water to shape the catalyst material” meansquantity of water required to make an acid peptized mixture of zeoliteand alumina powders into an extrudable mass.

The term “tabletting” as used herein refers to the process of forming acatalyst aggregate from zeolite powder or a mixture of zeolite andbinder powders by compressing the powder in a die.

The term “total base number or TBN” refers to the amount of baseequivalent to milligrams of KOH in one gram of sample. Thus, higher TBNnumbers reflect more alkaline products, and therefore a greateralkalinity reserve. The TBN of a sample can be determined by ASTM TestNo. D 2896 or any other similar procedure.

The term “total pore volume” obtained by Mercury Intrusion Porosimetryas used herein refers to the total pore volume in milliliters per gramderived from the graphical, cumulative pore volume distribution (Section14.1.6 of ASTM D 4284-03) or the corresponding tabular presentation ofthe same data.

As used herein, all percentages are weight percent, unless otherwisespecified.

As noted above, the present invention is directed to catalyst having acontrolled macropore structure comprising zeolite Y. The catalysts ofthe present invention were characterized by pore volume distributionobtained by Mercury Intrusion Porosimetry, ASTM Test No. D 4284-03.Mercury Intrusion Porosimetry provides a graph of cumulative pore volume(pv) versus pore diameter (pd). Mercury Intrusion Porosimetry also isused to determine the macropore peak diameter from the derivative, deltapv (Δpv) divided by delta pd (Δpd). The graphs are used to characterizethe catalysts of the present invention.

Zeolite Y catalysts and catalyst composites of the present inventionwhen used in alkylation of aromatic hydrocarbons with olefins exhibiteda substantial reduction in deactivation rates compared to zeoliticcatalysts known in the prior art. This result was unexpected, since ithad previously been believed that increasing the surface area of thecatalyst would increase its activity, but was likely to also increasedeactivation rates. Relative deactivation rates were determined for thecatalysts of the present invention under standard alkylation reactionsconditions. Results of the deactivation experiments are given in TableII. Reduction in deactivation rates of up to 75 percent and above wereobserved during alkylation reactions using these zeolitic Y catalystsand zeolite Y catalyst composites.

The zeolite Y catalysts and catalyst composites can be prepared usingzeolite Y CBV 760® or CBV 600® available from Zeolyst International.Samples of these zeolite Y materials from which catalysts and catalystcomposites of the present invention were prepared had a nominal silicato alumina ratio of ˜60:1 and ˜6.7:1, respectively. However, zeolite Yhaving a silica to alumina ratio between 5:1 and 120:1 may be used forthe preparation of the zeolite Y catalysts and catalyst composites ofthe present invention.

The zeolite Y catalysts of the present invention may be shaped or formedinto tablets, extrudates or any other shape using procedures well knownin the prior art. The preparation of extrudates requires the presence ofa binder, such as alumina. The tabletted catalysts do not require thepresence of a binder, but a binder may be present in a tabletted zeolitecatalyst. The crystalline zeolite powder may be compressed to form atablet. The tabletted catalysts of the present invention provideexceptionally low deactivation rates in alkylation reactions.

The alkylation reaction may be carried out by any conventionally knownprocess without the addition of water and using a dried aromatichydrocarbon and olefin feed. It is believed that the presence of waterduring the alkylation increases the deactivation rate of the catalystsof this invention. The aromatic hydrocarbon is reacted with one or moreolefins in the presence of a catalyst of the present invention underalkylation reaction conditions. The aromatic hydrocarbon may besingle-ring or double-ring, preferably the aromatic hydrocarbon is asingle-ring aromatic hydrocarbon. The aromatic hydrocarbon may be analkylated aromatic hydrocarbon, such as a mono-alkylated aromatichydrocarbon, wherein the alkyl group has from about 4 carbon atoms toabout 80 carbon atoms. When the aromatic hydrocarbon used is amono-alkylated aromatic, the product of the alkylation reaction is adi-alkylated aromatic.

The olefins useful for alkylation of the aromatic hydrocarbons may belinear-chain olefins or branched-chain olefins having from about 4carbon atoms to about 80 carbon atoms. In addition, normal alpha olefinsmay be isomerized to obtain partially-branched-chain olefins for use inalkylation reaction of the present invention. These resultingpartially-branched-chain olefins may be alpha-olefins, beta-olefins,internal-olefins, tri-substituted olefins, and vinylidene olefins.

Alkylated aromatic hydrocarbon sulfonic acids of the alkylated aromatichydrocarbons of the present invention may be prepared by any knownsulfonation reaction. The alkylated aromatic sulfonic acids may befurther reacted with an alkaline earth metal and carbon dioxide toobtain carbonated, overbased alkylated aromatic sulfonates useful asdetergents in lubricating oils. Carbonation may be carried out by anyconventionally known process. The degree of overbasing may be controlledby changing the reaction conditions and the amount of the alkaline earthmetal and carbon dioxide used in the carbonation process.

Procedure for Isomerization of Normal Alpha Olefins

The isomerization process may be carried out in batch or continuousmode. The process temperatures can range from 50° C. to 250° C. In thebatch mode, a typical method is to use a stirred autoclave or glassflask, which may be heated to the desired reaction temperature. Acontinuous process is most efficiently carried out in a fixed bedprocess. Space rates in a fixed bed process can range from 0.1 to 10 ormore weight hourly space velocity.

In a fixed bed process, the isomerization catalyst is charged to thereactor and activated or dried at a temperature of at least 150° C.under vacuum or flowing inert, dry gas. After activation, thetemperature of the isomerization catalyst is adjusted to the desiredreaction temperature and a flow of the olefin is introduced into thereactor. The reactor effluent containing the partially-branched,isomerized olefins is collected. The resulting partially-branched,isomerized olefins contain a different olefin distribution (alphaolefin, beta olefin; internal olefin, tri-substituted olefin, andvinylidene olefin) and branching content than the unisomerized olefin.

Procedure for Alkylation of Aromatic Hydrocarbons

Alkylation of aromatic hydrocarbons with normal alpha olefins,partially-branched-chain isomerized olefins, and branched-chain olefinsmay be carried out by any method known by a person skilled in the art.

The alkylation reaction is typically carried out with an aromatichydrocarbon and an olefin in molar ratios from 1:15 to 25:1. Processtemperatures can range from about 100° C. to about 250° C. The processis carried out without the addition of water. As the olefins have a highboiling point, the process is preferably carried out in the liquidphase. The alkylation process may be carried out in batch or continuousmode. In the batch mode, a typical method is to use a stirred autoclaveor glass flask, which may be heated to the desired reaction temperature.A continuous process is most efficiently carried out in a fixed bedprocess. Space rates in a fixed bed process can range from 0.01 to 10 ormore weight hourly space velocity.

In a fixed bed process, the alkylation catalyst is charged to thereactor and activated or dried at a temperature of at least 150° C.under vacuum or flowing inert, dry gas. After activation, the alkylationcatalyst is cooled to ambient temperature and a flow of the aromatichydrocarbon compound is introduced, optionally toluene. Pressure isincreased by means of a back pressure valve so that the pressure isabove the bubble point pressure of the aromatic hydrocarbon feedcomposition at the desired reaction temperature. After pressurizing thesystem to the desired pressure, the temperature is increased to thedesired reaction temperature. A flow of the olefin is then mixed withthe aromatic hydrocarbon and allowed to flow over the catalyst. Thereactor effluent comprising alkylated aromatic hydrocarbon, unreactedolefin and excess aromatic hydrocarbon compound are collected. Theexcess aromatic hydrocarbon compound is then removed by distillation,stripping, evaporation under vacuum, or any other means known to thoseskilled in the art.

Procedure for Sulfonation of Alkylated Aromatic Hydrocarbons

Sulfonation of alkylated hydrocarbons may be carried out by any methodknown by a person skilled in the art.

The sulfonation reaction is typically carried out in a falling filmtubular reactor maintained at about 65° C. The alkylated aromatichydrocarbon is placed in the tube and sulfur trioxide diluted withnitrogen is added to the alkylated aromatic hydrocarbon. The molar ratioof alkylated aromatic hydrocarbon to sulfur trioxide is maintained atabout 1.05:1. The resulting alkylated aromatic sulfonic acid may bediluted with about 10% 100 Neutral oil followed by thermal treatmentwith nitrogen bubbling at a rate of about 10 liters per kilogram ofproduct and stirring while maintaining the temperature at about 85° C.until the desired residual sulfuric acid content is obtained (maximum ofabout 0.5%).

Procedure for Carbonation, Overbasing of Alkylated Aromatic SulfonicAcids

Carbonation, overbasing of alkylaromatic sulfonic acids may be carriedout by any method known by a person skilled in the art to producealkylaromatic sulfonates.

Generally, the carbonation, overbasing reaction is carried out in areactor in the presence of the alkylated aromatic sulfonic acid, diluentoil, an aromatic solvent, and an alcohol. The reaction mixture isagitated and alkaline earth metal and carbon dioxide are added to thereaction while maintaining the temperature between about 20° C. and 80°C.

The degree of carbonation, overbasing may be controlled by the quantityof the alkaline earth metal and carbon dioxide added to the reactionmixture, the reactants and the reaction conditions used during thecarbonation process.

EXAMPLES Preparation of Zeolite Y Alkylation Catalyst Composite Example1 Preparation of Catalyst Composite 1

Zeolite Y alkylation catalyst composites were prepared by the followingmethod:

Loss-on-ignition (LOI) was determined for a sample of a commerciallyavailable zeolite Y CBV 760® available from Zeolyst International byheating the sample to 538° C. for 1 hour. The LOI obtained was 14.65weight % and provided the percent volatiles in the zeolite Y batch beingused. The LOI of a commercial sample of Versal® hydrated aluminum oxideavailable from Kaiser LaRoche Hydrate Partners was determined by heatingthe sample to 538° C. for 1 hour and was 24.87 weight %. Next, based onthe results obtained from the LOI, 1875 grams of zeolite Y powder and532 grams of alumina powder were weighed out to give a total of 1600grams of zeolite powder and 400 grams of alumina powder on avolatile-free basis. Extrusion aid, Methocell®, 60 grams, available fromDow Corning, was added to the mixture of the two powders.

The two dry powders were added to a Baker Perkins mixer and dry mixedfor 4 minutes. The amount of concentrated (70.7%) nitric acid to give0.7 weight % (based on 100% nitric acid) of the dry weight of thezeolite and the alumina powders was calculated to be 19.8 grams. Thisamount of 70.7% nitric acid was weighed out and dissolved in 200 gramsof deionized water.

The total amount of water and 70.7% nitric acid needed to obtain a finalconcentration of approximately 50% total volatiles was calculated asfollows. Volatiles in the Y zeolite powder are 274.67 grams (1874.67gram total weight−1600 grams dry weight). Volatiles in the aluminapowder are 232.40 grams (532.4 grams total weight−400 grams dry weight).Nitric acid solution and Methocell® extrusion aid are considered to be100% volatiles. Thus, if all the above raw materials were combined, thevolatiles would be 786.87 grams. To give a mixture of 2000 grams (1600grams zeolite and 400 grams alumina) dry powder with 50% volatiles, thetotal weight of the mixture must be 4000 grams. Thus, an additional1213.13 grams of deionized water must be added.

To the powders in the mixer, 1250 grams of deionized water were addedover a period of 5 minutes using a peristaltic pump. The mixer was thenstopped so that the walls of the mixer could be scraped down. Mixing wasthen resumed and the solution of nitric acid in water was added over 5minutes using the peristaltic pump. At the end of acid addition, mixingwas continued for a total time of 40 minutes, with occasional holds toallow for scraping the sides of the mixer. At the end of the mixingperiod, the mixture was still powdery and the volatiles were measured as48.83 weight %. Additional amounts of deionized water 10 grams at a timewere added with 5 minutes mixing for each addition until the mixtureappeared extrudable. A total of 85 grams of additional water was addedover 1 hour and 45 minutes. At this point, the volatiles were 48.36weight %.

The wet mixture was extruded through 1.27 millimeters, asymmetricquadrilobe die inserts, in a Bonnot extruder. The wet long cylindricalstrands were dried at 121° C. for 8 hours. The long cylindrical strandswere then broken to give extrudates with length to diameter ratio of2:6. The extrudates were sieved and the portion larger than 1 millimeterwas retained.

The extrudates were then calcined in a substantially dry environment ina muffle furnace using the following temperature program:

The extrudates were heated to 593° C. over two hours, then held at 593°C. for ½ hour and next cooled to 204° C. A total of 1681 grams ofextrudates were obtained.

Mercury Intrusion Porosimetry showed the extrudates to have a peakmacropore diameter of 1167 angstroms and a cumulative pore volume atdiameters less than 300 angstroms of 0.1400 ml/gram.

Example 2 Preparation of Catalyst Composite 2

Zeolite Y catalyst was prepared following the procedure used in Example1 above, with the following exceptions:

Catapal B® alumina available from Vista Chemical Company was usedinstead of Versal® alumina. The total amount zeolite Y and aluminapowders were scaled to 1300 grams dry weight. Methocell® extrusion aidwas not added. Volatiles of the zeolite powder and alumina powder were9.72 weight % and 24.82 weight %, respectively. Concentrated nitricacid, 12.9 grams, was dissolved in 300 grams deionized water. In theBaker Perkins mixer, 671.7 grams of deionized water were added in 10minutes, followed by the acid solution in 10 minutes. After mixing for40 minutes, volatiles were 47.18 weight %, but the mixture was too thickto extrude. With an additional 3 hours of mixing, the mixture was stillnot extrudable. Over the next 30 minutes, an additional 10 grams ofdeionized water was added. The mixture was then extruded, dried, andcalcined in a substantially dry environment.

Mercury Intrusion Porosimetry showed the peak macropore diameter to be878 angstroms and the cumulative pore volume at diameters less than 300angstroms to be 0.1424 ml/gram.

Example 3 Preparation of Catalyst Composite 3

This catalyst was made by the procedure described in Example 2 abovewith the following exceptions:

Volatiles of the zeolite Y powder and alumina powder were 12.24 weight %and 23.89 weight %, respectively. Corresponding amounts of zeolite andalumina powders were 1185 grams and 342 grams, respectively. Addeddeionized water was 580 grams. After 50 minutes of mixing, the mixturewas still granular. A good paste was obtained after mixing for 1 hour 30minutes. Volatiles were 46.8 weight % at extrusion time. Afterextruding, drying, sizing, and calcining in a substantially dryenvironment, Mercury Intrusion Porosimetry showed the peak macroporediameter to be 1006 angstroms and the cumulative pore volume atdiameters less than 300 angstroms to be 0.1400 ml/gram.

Example 4 Preparation of Catalyst Composite 4

This catalyst was made by the procedure described in Example 2 with thefollowing exceptions:

Volatiles of the zeolite Y powder and alumina powder were 14.36 weight %and 27.54 weight %, respectively. Corresponding amounts of zeolite andalumina powders were 747.4 grams and 220.8 grams, respectively. Thefinal weight % of the nitric acid of the dry weight of the zeolite andthe alumina in this preparation was 0.75%. The acid was dissolved in655.8 grams of deionized water. The powders were mixed in a plastic bagfor 3 minutes and then mixed in the Baker Perkins mixer for 3 minutes.The acid solution was pumped in over 8 minutes while continued mixing.At 10 minutes after completion of acid addition, the mixture becamepasty. Mixing was continued for an additional 30 minutes. Volatiles were49.0 weight %. The wet mix was extruded, dried, and sized.

The extrudates were calcined in a substantially dry environment in amuffle furnace according to the following temperature program:

The extrudates were heated at full power to 593° C. Temperatureovershoot was avoided. Next, the extrudates were held at 593° C. for onehour and cooled to 149° C. Mercury Intrusion Porosimetry showed the peakmacropore diameter to be 1486 angstroms and the cumulative pore volumeat diameters less than 300 angstroms to be 0.1494 ml/gram.

Example 5 Preparation of Catalyst 5

Tabletted zeolite Y catalyst was prepared by a custom catalystmanufacturer using a sample of the zeolite Y CBV 760® available fromZeolyst International. The tablets were cylinders, ⅛ inch in diameterand approximately ⅛ inch in length. Mercury Intrusion Porosimetry showedthe peak macropore diameter to be 815 angstroms and the cumulative porevolume at diameters less than 300 angstroms to be 0.0844 ml/gram.

Example 6 Preparation of Catalyst 10

This catalyst was made by the procedure described in Example 2 with thefollowing exceptions:

Volatiles of the zeolite Y powder and alumina powder were 18.7 weight %and 26.5 weight %, respectively. Corresponding amounts of zeolite andalumina powders were 639.6 grams and 276.9 grams, respectively. Thefinal weight % of the nitric acid of the dry weight of the zeolite andthe alumina in this preparation was 0.75% and 6.44 grams of nitric acidwas dissolved in 150 grams of deionized water. The powders were mixed ina plastic bag for 15 minutes and then mixed in the Baker Perkins mixerfor 10 minutes. An additional 276.9 grams of deionized water was pumpedinto the mixture over 20 minutes while mixing. The acid solution waspumped in over 8 minutes with continued mixing. Mixing was continued foran additional 30 minutes. Volatiles were 46.40 weight %. The wet mix wasextruded, dried, and sized. The extrudates were calcined in asubstantially dry environment in a muffle furnace according to thefollowing temperature program:

The extrudates were heated at full power to 593° C. Temperatureovershoot was avoided. Next, the extrudates were held at 593° C. for onehour and cooled to 149° C. Mercury Intrusion Porosimetry showed the peakmacropore diameter to be 941 angstroms and the cumulative pore volume atdiameters less than 300 angstroms to be 0.155 ml/gram.

Example 7 Preparation of Catalyst 12

This catalyst was made by the procedure described in Example 2 with thefollowing exceptions:

Volatiles of the zeolite powder and alumina powder were 12.24 weight %and 23.89 weight %, respectively. Corresponding amounts of zeolite andalumina powders were 1185.1 grams and 341.6 grams, respectively. Thefinal weight % of the nitric acid of the dry weight of the zeolite andthe alumina in this preparation was 0.75% and 12.9 grams of nitric acidwas dissolved in 300 grams of deionized water. The powders were mixed ina plastic bag for 5 minutes and then mixed in the Baker Perkins mixerfor 5 minutes. Additional deionized water, 619.7 grams, was added to themixture over 20 minutes. The acid solution was pumped in over 8 minuteswith continued mixing. Mixing was continued for an additional 40minutes. At this time, the mixture was still a powder. After 3 hours ofmixing, an additional 50 grams of deionized water was added to themixture. After 3-½ hours of mixing, an additional 25 grams of deionizedwater was added to the mixture and another 15 grams of deionized waterwas added to the mixture after 4 hours and 4-¼ hours of mixing. After 4hours and 55 minutes of mixing, the volatiles were 45.2 weight %. Thewet mix was extruded, dried, and sized.

The extrudates were calcined in a substantially dry environment in amuffle furnace according to the following temperature program:

The extrudates were heated at full power to 593° C. Temperatureovershoot was avoided. Next, the extrudates were held at 593° C. for onehour and cooled to 149° C. Mercury Intrusion Porosimetry showed the peakmacropore diameter to be 900 angstroms and the cumulative pore volume atdiameters less than 300 angstroms to be 0.144 ml/gram.

The Mercury Intrusion Porosimetry results for the zeolite Y catalysts ofExamples 1-7 (Catalyst Composites 1-5, 10 and 12) are given below inTable I.

TABLE I Mercury Intrusion Porosimetry Properties Macropore peak CatalystTotal PV* PV < 300 angstroms** diameter Composite (ml/gram) (ml/gram)(angstroms) 1 0.4612 0.140 1167 2 0.4207 0.142 878 3 0.4208 0.140 1006 40.4492 0.149 1486   5*** 0.3914 0.084 815 10  0.403 0.155 941 12  0.3990.144 900 *Total pore volume. **Total pore volume at diameters less thanor equal to 300 angstroms. ***Catalyst 5 is not a composite. Catalyst 5is a tabletted zeolite Y powder, prepared as described above in Example5.

Example 8 Preparation of Isomerized Normal Alpha Olefins

Typically, isomerization of normal alpha olefins is carried out asdescribed below:

C₂₀-C₂₄ normal alpha olefin with the following composition was used forthis Example:

-   -   Alpha olefin 89.1%    -   Beta olefin 0.5%    -   Internal olefin 1.4%    -   Tri-substituted olefin 0.2%    -   Vinylidene olefin 9.5% (determined by carbon nuclear magnetic        resonance spectroscopy)    -   Branched-chain olefin 11% (determined by infra red spectroscopy)

The normal alpha olefin was pumped up-flow through a fixed-bed reactor(570 millimeters high and with an inside diameter of 22.3 millimeters)containing 65 grams of solid olefin isomerization. The reactor wasoperated isothermally at 160° C. at a liquid to hourly space velocity of0.5 per hour and at atmospheric pressure.

The reactor effluent containing the partially branched, isomerizedolefin is collected. The resulting partially-branched, isomerized olefincontains a different olefin distribution (alpha-olefin, beta-olefin;internal-olefin, tri-substituted-olefin, and vinylidene-olefin) andbranching content than the un-isomerized olefin.

Example 9 Preparation of Alkylbenzene Compositions

Typically, alkylation of aromatic hydrocarbons with normal alphaolefins, partially-branched-chain isomerized olefins and branched-chainolefins was carried out as described below:

A fixed bed reactor constructed from 15.54 millimeters internal diameterSchedule 160 stainless steel pipe was used for this alkylation test.Pressure in the reactor was maintained by an appropriate back pressurevalve. The reactor and heaters were constructed so that adiabatictemperature control could be maintained during the course of alkylationruns. A 192 gram bed of 850 micrometer to 2 millimeters Alundumparticles was packed in the bottom of the reactor to provide a pre-heatzone. Next, 100 grams of Catalyst Composite 12 was charged to the fixedbed reactor. The reactor was gently vibrated during loading to give amaximum packed bulk density of catalyst in the reactor. Finally, voidspaces in the catalyst bed were filled with 351 grams 150 micrometersAlundum particles as interstitial packing.

The reactor was then closed, sealed, and pressure tested under nitrogen.Next the alkylation catalyst was dehydrated during 15 hours at 200° C.under a 20 liters per hour flow of nitrogen measured at ambienttemperature and pressure and then cooled to 100° C. under nitrogen.Benzene was then introduced into the catalytic bed in an up-flow mannerat a flow rate of 195 grams per hour. Temperature (under adiabatictemperature control) was increased to a start-of-run temperature of 182°C. (measured just before the catalyst bed) and the pressure wasincreased to 14.6 atmospheres.

When temperature and pressure had lined out at desired start-of-runconditions of 182° C. and 14.6 atmospheres, a feed mixture, consistingof benzene and C₂₀₋₂₄ NAO at a molar ratio of 10:1 and dried overactivated alumina, was introduced in an up-flow manner. As the feedreached the catalyst in the reactor, reaction began to occur andinternal catalyst bed temperatures increased above the inlettemperature. After about 8 hours on-stream, the reactor exotherm was 20°C. At 26 hours on-stream, the olefin conversion in the product was99.1%. The run was stopped after 408 hours on-stream, although the runcould have continued. At this time, the olefin conversion was 99.45%.

Alkylated aromatic hydrocarbon products containing excess benzene werecollected during the course of the run. After distillation to removeexcess aromatic hydrocarbon, analysis showed that greater than 99%conversion of olefin was achieved during the course of the run.

Example 10 Preparation of Alkylated Benzene Sulfonic Acids

The alkylbenzene alkylate produced as in Example 9 above was sulfonatedby a concurrent stream of sulfur trioxide (SO₃) and air with in atubular reactor (2 meters long and 1 centimeter inside diameter) in adown flow mode using the following conditions:

Reactor temperature was 60° C., SO₃ flow rate was 73 grams per hour,alkylate flow rate was 327 grams per hour at a SO₃ to alkylate molarratio of 1.05. The SO₃ was generated by passing a mixture of oxygen andsulfur dioxide (SO₂) through a catalytic furnace containing vanadiumoxide (V₂O₅).

The resulting crude alkylbenzene sulfonic acid had the followingproperties based on the total weight of the product: the weight % ofHSO₃ was 16.1 and the weight % of H₂SO₄ was 1.35.

The crude alkylbenzene sulfonic acid was diluted with 10 weight % 100Neutral diluent oil based on the total weight of the crude alkylbenzenesulfonic acid and placed in a four liter four-neck glass reactor fittedwith a stainless steel mechanical agitator rotating at between 300 and350 rpm, a condenser and a gas inlet tube (2 millimeters insidediameter) located just above the agitator blades for the introduction ofnitrogen gas. The contents of the reactor was heated to 85° C. withstirring and nitrogen gas was bubbled through the mixture between 30-40liters per hour for between about 4 to 6 hours until the weight % ofH₂SO₄ is less than about 0.3 weight % based on the total weight of theproduct. This material is the final alkylbenzene sulfonic acid.

The final alkylbenzene sulfonic acid had the following properties basedon the total weight of the product: weight % of HSO₃ was 15.76 andweight % of H₂SO₄ was 0.15.

Example 11 Preparation of Carbonated, Overbased Alkylated BenzeneSulfonates

To a 5 liter four-neck reactor equipped with heating and coolingcapability and fitted with a stainless steel mechanical agitatorrotating at between 300 and 350 rpm, a gas inlet tube (2 millimetersinside diameter) located just above the agitator blades for the additionof CO₂, a distillation column and condenser under nitrogen gas wascharged 123.7 grams of centrate.

The centrate was a mixture of the sludge fractions previously producedduring the purification of high TBN carbonated, overbased syntheticsulfonates by centrifugation and decantation and was added to thereaction mixture of this example for recycling the contents of thecentrate. The centrate had a TBN of 206 and contained approximately 68grams of xylene solvent, 11 grams active calcium sulfonate, 8 gramscalcium hydroxide and calcium carbonate, 8 grams of carbon dioxide, and22 grams of 100 Neutral diluent oil isolated.

Next, 40 grams of methanol, 207 grams of xylene solvent, 281 grams (0.59mole) of the alkylbenzene sulfonic acid (HSO₃ was 15.8 weight % based onthe total weight of the reaction mixture) from Example 10 above wascharged to the reactor over 15 minutes at room temperature. A slurry of160 grams (2.16 mole) of calcium hydroxide, 365 grams of xylene solvent,and 94.2 grams of methanol was added to the reactor and the reactor wascooled to 25° C. Next, 35 grams (0.79 mole) of CO₂ was added to thereaction mixture through the gas inlet tube over 39 minutes while thetemperature of the reactor increased to about 32° C. A second slurrycomposed of 160 grams (2.16 mole) of calcium hydroxide, 384 grams xylenesolvent, and 131 grams of methanol was then added to the reactorconcurrently with 0.9 grams of CO₂ over about 1 minute. Next, 92 gramsof CO₂ was added to the reactor over 64 minutes while the temperature ofthe reactor increased from about 30° C. to 41° C. A third slurrycomposed of 82 grams of calcium hydroxide and 298 grams of xylenesolvent was then charged to the reactor concurrently with 1.4 grams ofCO₂ over about 1 minute. Next, 55 grams (1.25 mole) of CO₂ was added tothe reactor over approximately 60 minutes while keeping the reactortemperature at approximately 38° C.

The water and methanol were then distilled from the reactor by firstheating the reactor to 65° C. over 40 minutes at atmospheric pressure,then to 93° C. over 60 minutes at atmospheric pressure, and then 130° C.over 30 minutes at atmospheric pressure. The temperature of the reactorwas then decreased to 110° C. over 60 minutes at atmospheric pressureand next held at 110° C. for 30 minutes at atmospheric pressure. Thecontents of the reactor were then cooled to approximately 30° C. and 510grams of 600 Neutral diluent oil was added to the reactor followed by413 grams of xylene solvent. The sediment in the product was thenremoved by centrifugation. The xylene solvent in the product wasdistilled by heating the product to 204° C. over approximately 45minutes at 30 millimeters Hg vacuum and holding the product at 204° C.and 30 millimeters Hg vacuum for 10 minutes. The vacuum was replacedwith nitrogen gas and the contents were allowed to cool to roomtemperature to afford the carbonated, overbased sulfonate with thefollowing properties based on the total weight of the product:

Weight % calcium was 16.1, TBN was 424, weight % of sulfur was 1.81,weight % of calcium sulfonate was 0.87, and viscosity was 101 cSt at100° C.

Example 12 Procedure for Measuring Deactivation Rates of the Catalystsin Alkylation Reactions

Deactivation rates of the alkylation catalysts were measured during thealkylation reaction similar to the alkylation reaction in Example 9above.

The alkylation reaction was carried out as described above underadiabatic temperature control. As the alkylation reaction wasexothermic, a temperature exotherm was measured by means ofappropriately located thermocouples in the catalyst bed. Usingtemperature profile data from a catalyst run, the position of thetemperature exotherm in the bed was plotted as a function of time, inhours. The deactivation rate of the catalyst is the slope of this linein centimeters per hour. All catalysts were evaluated at standardconditions of temperature, pressure, and space velocity and thedeactivation rates were measured.

Catalyst Composites 1, 2, 4, 5, 10 and 12 are the Catalyst Compositesprepared in Examples 1-7 and shown in Table I above with the exceptionthat Catalyst Composite 2 in Table II is a mixture of batches ofCatalyst Composite 2 in Table I.

Test 1 was conducted during alkylation of toluene with an isomerized C₂₀to C₂₄, low alpha content olefin at a temperature of 170° C. The molarratio of toluene to olefin was 6.

Test 2 was conducted during alkylation of benzene with a C₂₀ to C₂₄normal alpha olefin at a temperature of 180° C. The molar ratio oftoluene to olefin was 10.

Deactivation rates are shown relative to the deactivation rate ofCatalyst Composite 8 and Catalyst Composite 11 and are given in Table IIbelow.

TABLE II Mercury Intrusion Porosimetry Properties Relative % zeoliteNominal Macropore Deactivation Catalyst in Zeolite Total PV* PV < 300 Åpeak Rate Composite Catalyst SAR* (ml/gram) (ml/gram) diameter, Å Test 1Test 2  1 80 60 0.461 0.140 1167 86 —   2** 80 60 0.436 0.156 931 61 46 4 80 60 0.449 0.149 1486 — 50  5 100 60 0.391 0.084 815 — 23  6 80 600.596 0.182 1664 67 —  7 65 6.7 0.488 0.270 1376 90 —  8 70 6.7 0.4650.200 1591 100  —  9 80 60 0.575 0.174 1513 73 — 10 80 60 0.403 0.155941 35 — 11 80 60 0.463 0.179 1110 43 — 12 80 60 0.399 0.144 900 — 35 1380 60 0.449 0.163 1157 — 48 14 80 60 0.404 0.146 962 — 46 15 80 60 0.5050.155 1738 — 100  16 80 60 0.444 0.162 1244 — 54 17 80 60 0.415 0.1621031 — 46 18 80 60 0.421 0.136 1256 — 38 *Silica to alumina ratio in thecrystalline zeolite powder. **Catalyst Composite 2 in Table II wasprepared as the Catalyst Composite 2 in Table I, except that CatalystComposite 2 in Table II contained more than one batch of catalystscomposites prepared in the manner of Catalyst Composite 2 of Table I.

Effect of Silica to Alumina Ratio on Reduction in Deactivation Rate

Without being bound by any theory, it is believed that the higher silicato alumina ratio and percent zeolite in the catalyst are important forobtaining greater degree of reduction in relative deactivation rateswith the catalyst composites of this invention. In Table II, Catalysts 6and 8 have similar macropore peak diameters and cumulative pore volumes,but very different silica to alumina ratios. By increasing the silica toalumina ratio from 6.7 to 60 and percent zeolite from 70 percent to 80percent, the relative deactivation rate of 100 of Catalyst 8 is reducedto 67 of Catalyst 6.

TABLE III Mercury Intrusion Porosimetry Properties Relative % zeoliteNominal Macropore Deactivation Catalyst in Zeolite Total PV* PV < 300 Åpeak Rate Composite Catalyst SAR* (ml/gram) (ml/gram) diameter, Å Test 16 80 60 0.596 0.182 1664 67 8 70 6.7 0.465 0.200 1591 100

Effect of Peak Macropore Diameter on Reduction in Deactivation Rate

Without being bound by any theory, it is believed that the peakmacropore diameter has an effect on the deactivation rate of thecatalyst composites of this invention. A higher peak macropore diameterresults is a higher relative deactivation rate. In Table IV, CatalystComposites 9 and 10 are compared because, although they both differslightly in the cumulative pore volume, 174 versus 155, CatalystComposite 9 has a much higher peak macropore diameter and a much higherrelative deactivation rate, 1513 and 73, compared to Catalyst Composites10, 941, and 35.

TABLE IV Mercury Intrusion Porosimetry Properties Relative NominalMacropore Deactivation Catalyst % zeolite Zeolite Total PV* PV < 300 Åpeak Rate Composite in Catalyst SAR* (ml/gram) (ml/gram) diameter, ÅTest 1 9 80 60 0.575 0.174 1513 73 10 80 60 0.403 0.155 941 35

Effect of Cumulative Pore Volume on Deactivation Rate

Without being bound by any theory, it is believed that lowering thecumulative pore volume at pore diameters less than or equal to 300angstroms results in lower deactivation rates. In Table V, CatalystComposites 16 and 18 differ only by the cumulative pore volume, 162 and136, respectively, and Catalyst Composite 16 has a higher relativedeactivation rate, 54, compared to Catalyst Composites 18, 38.

TABLE V Mercury Intrusion Porosimetry Properties Relative NominalMacropore Deactivation Catalyst % zeolite Zeolite Total PV* PV < 300 Åpeak Rate Composite in Catalyst SAR* (ml/gram) (ml/gram) diameter, ÅTest 2 16 80 60 0.444 0.162 1244 54 18 80 60 0.421 0.136 1256 38

1. An alkylated aromatic composition prepared by the process comprisingcontacting at least one aromatic hydrocarbon with at least one olefinunder alkylation conditions in the presence of a catalyst having amacropore structure comprising zeolite Y wherein the peak macroporediameter, measured by ASTM Test No. D 4284-03, is less than about 2000angstroms and the cumulative pore volume of the catalyst at porediameters less than or equal to about 500 angstroms, measured by ASIMTest No. D 4284-03, is less than or equal to about 0.30 milliliters pergram.
 2. The alkylated aromatic composition of claim 1, wherein thearomatic hydrocarbon moiety on the alkylated aromatic composition isbenzene or toluene.
 3. The alkylated aromatic composition of claim 2,wherein the aromatic hydrocarbon moiety on the alkylated aromaticcomposition is toluene.
 4. The alkylated aromatic composition of claim1, wherein the olefin employed to prepare the alkylated aromaticcomposition is an alpha olefin, an isomerized olefin, a branched-chainolefin or mixtures thereof.
 5. The alkylated aromatic composition ofclaim 4, wherein the olefin has from about 4 carbon atoms to about 80carbon atoms.
 6. The alkylated aromatic composition of claim 5, whereinthe alpha olefin or the isomerized olefin have from about 6 carbon atomsto about 40 carbon atoms.
 7. The alkylated aromatic composition of claim6, wherein alpha olefin or the isomerized olefin have from about 20carbon atoms to about 40 carbon atoms.
 8. The alkylated aromaticcomposition of claim 4, wherein the branched-chain olefin has from about6 carbon atoms to about 70 carbon atoms.
 9. The alkylated aromaticcomposition of claim 8, wherein the branched-chain olefin has from about8 carbon atoms to about 50 carbon atoms.
 10. The alkylated aromaticcomposition of claim 9, wherein the branched-chain olefin has from about12 carbon atoms to about 18 carbon atoms.
 11. The alkylated aromaticcomposition of claim 4, wherein the olefin is a partially-branched-chainisomerized olefin wherein the olefin has from about 6 carbon atoms toabout 40 carbon atoms.
 12. The alkylated aromatic composition of claim11, wherein the Partially-branched-chain isomerized olefin has fromabout 20 carbon atoms to about 40 carbon atoms.
 13. The alkylatedaromatic composition of claim 1, wherein the alkylated aromaticcomposition is sulfonated to form an alkylated aromatic sulfonic acid.14. The alkylated aromatic composition of claim 2, wherein the alkylatedaromatic sulfonic acid is reacted with an alkaline earth metal andcarbon dioxide to produce a carbonated, overbased alkylated aromaticsulfonate.
 15. An alkylated aromatic composition prepared by the processcomprising contacting at least one aromatic hydrocarbon with at leastone olefin under alkylation conditions in the presence of a catalystcomposite, wherein the peak macropore diameter of the catalyst, measuredby ASTM Test No. D 4284-03, is less than about 2000 angstroms and thecumulative pore volume of the catalyst at pore diameters less than orequal to about 500 angstroms, measured by ASTM Test No. D 4284-03, isless than or equal to about 0.30 milliliters per gram, and wherein thecatalyst composite comprises: (a) a zeolite Y; and (b) a binder.
 16. Thealkylated aromatic composition of claim 15, wherein the aromatichydrocarbon moiety on the alkylated aromatic composition is benzene ortoluene.
 17. The alkylated aromatic composition of claim 16, wherein thearomatic hydrocarbon moiety on the alkylated aromatic composition istoluene.
 18. The alkylated aromatic composition of claim 15, wherein theolefin employed to prepare the alkylated aromatic composition is analpha olefin, an isomerized olefin, a branched-chain olefin or mixturesthereof.
 19. The alkylated aromatic composition of claim 18, wherein theolefin has from about 4 carbon atoms to about 80 carbon atoms.
 20. Thealkylated aromatic composition of claim 19, wherein the alpha olefin orthe isomerized olefin have from about 6 carbon atoms to about 40 carbonatoms.
 21. The alkylated aromatic composition of claim 20, wherein alphaolefin or the isomerized olefin have from about 20 carbon atoms to about40 carbon atoms.
 22. The alkylated aromatic composition of claim 18,wherein the branched-chain olefin has from about 6 carbon atoms to about70 carbon atoms.
 23. The alkylated aromatic composition of claim 22,wherein the branched-chain olefin has from about 8 carbon atoms to about50 carbon atoms.
 24. The alkylated aromatic composition of claim 23,wherein the branched-chain olefin has from about 12 carbon atoms toabout 18 carbon atoms.
 25. The alkylated aromatic composition of claim18, wherein the olefin is a partially-branched-chain isomerized olefinwherein the olefin has from about 6 carbon atoms to about 40 carbonatoms.
 26. The alkylated aromatic composition of claim 25, wherein thepartially-branched-chain isomerized olefin has from about 20 carbonatoms to about 40 carbon atoms.
 27. The alkylated aromatic compositionof claim 15, wherein the alkylated aromatic composition is sulfonated toform an alkylated aromatic sulfonic acid.
 28. The alkylated aromaticcomposition of claim 27, wherein the alkylated aromatic sulfonic acid isreacted with an alkaline earth metal and carbon dioxide to produce acarbonated, overbased alkylated aromatic sulfonate.
 29. An alkylatedaromatic composition prepared by the process comprising contacting atleast one aromatic hydrocarbon with at least one olefin under alkylationconditions in the presence of a catalyst comprising zeolite Y, whereinthe catalyst is in the form of a tablet.